Synthesis of crystalline silicate MCM-47

ABSTRACT

This invention relates to a new form of crystalline material identified as zeolite MCM-47, to a new and useful improvement in synthesizing said crystalline material and to use of said crystalline material prepared in accordance herewith as a catalyst for organic compound, e.g. hydrocarbon compound, conversion.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is related in scope of subject matter to U.S.application Ser. No. 07/682,044 filed on even date herewith.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a new and useful improvement in synthesizing acrystalline silicate identified as MCM-47, the new MCM-47 synthesized,and use of the crystalline material synthesized in accordance herewithas a catalyst component for organic compound, e.g. hydrocarbon compound,conversion.

More particularly, this invention relates to an improved method forpreparing the crystalline MCM-47 structure whereby synthesis isfacilitated and reproducible and the product exhibits high purity andcatalytic utility.

2. Discussion of the Prior Art

Crystalline silicate MCM-47 and its conventional preparation is taughtby U.S. Pat. No. 4,637,923, the entire disclosure of which isincorporated herein by reference. It has a distinctive X-ray diffractionpattern which identifies it from other known crystalline materials.

Lok et al. (3 Zeolites, 282-291 (1983)) teach numerous organic compoundswhich act as directing agents for synthesis of various crystallinematerials, such as, for example, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35,ZSM-48, AlPO₄ -5, AlPO₄ -8, AlPO₄ -20 and others. The article does notshow the presently required organic for synthesis of MCM-47. Thezeolitic compositions labeled "PSH-3" in U.S. Pat. No. 4,439,409 aresynthesized from reaction mixtures containing hexamethyleneimine asdirecting agent. U.S. Pat. No. 4,954,325 utilizes hexamethyleneimine inanother reaction mixture to direct synthesis of MCM-22. That organic isused in U.S. Pat. No. 4,981,663 for synthesis of yet another crystallinestructure labelled MCM-35.

U.S. Pat. No. 4,391,785 teaches a method for synthesis of zeolite ZSM-12from a reaction mixture comprising, as a directing agent, a compoundselected from the group consisting of dimethyl pyridinium halide anddimethyl pyrrolidinium halide. U.S. Pat. No. 4,296,083 claimssynthesizing zeolites characterized by a Constraint Index of 1 to 12 andan alumina/silica mole ratio of not greater than 0.083 from a specifiedreaction mixture containing an organic nitrogen-containing cationprovided by an amine identified as being selected from the groupconsisting of triethylamine, trimethylamine, tripropylamine,ethylenediamine, propanediamine, butanediamine, pentanediamine,hexanediamine, methylamine, ethylamine, propylamine, butylamine,dimethylamine, diethylamine, dipropylamine, benzylamine, aniline,pyridine, piperidine and pyrrolidine.

U.S. Pat. No. 4,151,189 claims a method for synthesizing zeolites ZSM-5,ZSM-12, ZSM-35 and ZSM-38 containing an organic nitrogen cation from aspecified reaction mixture containing a primary amine having 2 to 9carbon atoms as a directing agent. U.S. Pat. No. 4,112,056 teaches asynthesis method for ZSM-12 from a reaction mixture containingtetraethylammonium ions as directing agent. U.S. Pat. No. 4,452,769claims a method for synthesizing ZSM-12 from a reaction mixturecontaining methyltriethylammonium ions as the directing agent. EuropeanPatent Application 13,630 claims synthesis of ZSM-12 from a reactionmixture containing a directing agent define as an organic compoundcontaining nitrogen and comprising "an alkyl or aryl group havingbetween 1 and 7 carbon atoms, at least one of which comprises an ethylradical".

Other publications teaching various organic directing agents forsynthesis of various crystalline materials include, for example, U.S.Pat. No. 4,592,902, teaching use of an alkyltropinium directing agent,alkyl being of 2 to 5 carbon atoms, for synthesis of ZSM-5; U.S. Pat.No. 4,640,829 teaching use of dibenzyldimethylammonium directing agentfor synthesis of ZSM-50; U.S. Pat. No. 4,637,923, teaching use of (CH₃)₂(C₂ H₅)N⁺ (CH₂)₄ N⁺ (C₂ H₅)(CH₃)₂ directing agent for synthesis ofanother novel zeolite; U.S. Pat. No. 4,585,747, teaching use of bis(N-methylpyridyl) ethylinium directing agent for synthesis of ZSM-48;U.S. Pat. No. 4,585,746, teaching use of bis (N-methylpyridyl)ethylinium directing agent for synthesis of ZSM-12; U.S. Pat. No.4,584,286, teaching use of bis (N-methylpyridyl) ethylinium directingagent for synthesis of ZSM-35; U.S. Pat. No. 4,568,654, teaching use ofcobalticinium, dimethylpiperidinium, trimethylene bis trimethylammoniumor tetramethylpiperazinium directing agents for synthesis of ZSM-51;U.S. Pat. No. 4,559,213, teaching use of DABCO-C₄₋₁₀ -diquat directingagent for synthesis of ZSM-12; U.S. Pat. No. 4,482,531, teachingsynthesis of ZSM-12 ;with a DABCO-C_(n) -diquat, n being 4,5,6 or 10,directing agent; and U.S. Pat. No. 4,539,193, teaching use of bis(dimethylpiperidinium) trimethylene directing agent for synthesis ofZSM-12.

U.S. Pat. No. 4,139,600 teaches a method for synthesis of zeolite ZSM-5from a reaction mixture comprising, as a directing agent, analkyldiamine. U.S. Pat. No. 4,341,748 shows synthesis of ZSM-5 structurefrom reaction mixtures comprising ethanol, ZSM-5 seeds, ethanol andseeds, ethanol and ammonimum hydroxide, and ethanol, ammonium hydroxideand ZSM-5 seeds. U.S. Pat. No. 4,100,262 teaches synthesis of ZSM-5 froma reaction mixture comprising a tetraalkylammonium source and atetraureacobalt (II) complex.

Various diquaternary ammonium compounds have been identified asdirecting agents for a particular assortment of crystalline materials.For instance, U.S. Pat. Nos. 4,490,342 and 4,619,820 show synthesis ofZSM-23 from a reaction mixture containing the organic of U.S. Pat. No.4,531,012, i.e. (CH₃)₃ N⁺ (R)N⁺ (CH₃)₃, where R is a saturated orunsaturated hydrocarbon having 7 carbon atoms. U.S. Pat. No. 4,665,250teaches the use of linear diquaternary ammonium compounds of thestructure (CH₃)₃ N⁺ (CH₂)_(m) N⁺ (CH₃)₃, m being 5, 6, 8, 9 or 10, forsynthesis of ZSM-48. U.S. Pat. No. 4,623,527 teaches numerousdiquaternary ammonium compounds and shows use of (CH₃)₃ N⁺ (CH₂)₇ N⁺(CH₃)₃ directing agent for synthesis of MCM-10.

U.S. Pat. No. 4,632,815 teaches numerous diquaternary ammonium compoundsand shows use of (CH₃)₃ N⁺ (CH₂)₄ N⁺ (CH₃)₃ to direct synthesis of aSilica-X structure type. U.S. Pat. No. 4,585,639 teaches use of thediquaternary (C₂ H₅)(CH₃)₂ N⁺ (CH₂) _(4or6) N⁺ (CH₃)₂ (C₂ H₅ asdirecting agent for synthesis of ZSM-12. Synthesis of ZSM-5 is directedby the diquaternary (alkyl)₃ N⁺ (CH₂)₆ N⁺ (alkyl)₃, alkyl being propylor butyl, in U.S. Pat. No. 4,585,638.

EPA 42,226 and U.S. Pat. No. 4,537,754 teach existence of numerousdiquaternary ammonium compounds, but show use of (CH₃)₃ N⁺ (CH₂)₆ N⁺(CH₃)₃ as directing agent for synthesis of EU-1. EPA 51,318 teaches useof the same diquaternary for synthesis of TPZ-3. It is noted that EU-1,TPZ-3 and ZSM-50 have the same structure.

Applicant knows of no prior art method for preparing a crystallineMCM-47 structure utilizing the present method.

SUMMARY OF THE INVENTION

An improved, economical and reproducible method for preparing acrystalline silicate identified as zeolite MCM-47 exhibiting highpurity, catalytic activity and other valuable properties is provided.The method comprises forming a reaction mixture hydrogel containingsources of alkali or alkaline earth metal (M) cations; an oxide oftrivalent element (X), e.g. aluminum, boron, iron, gallium, indium andmixtures thereof; an oxide of tetravalent element (Y), e.g. silicon,germanium, tin and mixtures thereof; bis(methylpyrrolidinium)-DIQUAT-4directing agent (R); and water, said reaction mixture having acomposition in terms of mole ratios, within the following ranges:

    ______________________________________                                        Reactants     Useful       Preferred                                          ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                   200 to ∞                                                                             300 to 10,000                                      H.sub.2 O/YO.sub.2                                                                          5 to 400     20 to 100                                          OH.sup.-- /YO.sub.2                                                                         0 to 1.0     0.05 to 0.4                                        M/YO.sub.2    0 to 2.0     0.10 to 1.0                                        R/YO.sub.2    0.005 to 2.0 0.05 to 1.0                                        ______________________________________                                    

The method further comprises maintaining the reaction mixture untilcrystals of the MCM-47 of structure are formed. Reaction conditionsrequired consist of heating the foregoing reaction mixture to atemperature of from about 60° C. to about 230° C. for a period of timeof from about 6 hours to about 20 days. A more preferred temperaturerange is from about 100° C. to about 200° C. with the amount of time ata temperature in such range being from about 2 days to about days. Thesolid product comprising MCM-47 crystals is recovered from the reactionmedium, as by cooling the whole to room temperature, filtering and waterwashing.

EMBODIMENTS

The particular effectiveness of the presently required organic directingagent having a 4-carbon methylene chain length, when compared with otherdirecting agents, such as those identified above, for the presentsynthesis is believed due to its ability to function as a template inthe nucleation and growth of MCM-47 crystals from the above high YO₂,e.g. SiO₂, high alkalinity, e.g. low OH⁻⁻ /YO₂, reaction mixture. Thisis true even though no predigestion of the gel is required prior tocrystallization. When the organic template has a shorter methylene chainlength, such as bis(methylpyrrolidinium)-DIQUAT-3, MCM-47 is no longercrystallized. This different organic directing agent functions in thisfashion in the reaction mixture having the above described compositionand under the above described conditions of temperature and time.

The crystalline product of the present method has a YO₂ /X₂ O₃, e.g.SiO₂ /Al₂ O₃, molar ratio within a rather broad range of from about 200to greater than about 2000.

It should be noted that the ratio of components of the reaction mixturerequired herein are critical to achieve maximum effectiveness. Forinstance, if the YO₂ /X₂ O₃ ratio is less than about 180, anotherzeolite phase will form. In general, with higher YO₂ /X₂ O₃ ratios inthe reaction mixture, crystallization of MCM-47 proceeds in a timely,efficient manner.

The synthesis of the present invention is facilitated when the reactionmixture comprises seed crystals, such as those having the structure ofMCM-47. The use of at least 0.01%, preferably about 0.10%, and even morepreferably about 1% seed crystals (based on total weight) of crystallinematerial will be useful.

The reaction mixture composition for the synthesis of MCM-47 crystalshereby can be prepared utilizing materials which can supply theappropriate oxide. The useful sources of X₂ O₃, e.g. aluminum oxide,include, as non-limiting examples, any known form of such oxide, e.g.aluminum oxide or hydroxide, organic or inorganic salt or compound, e.g.alumina and aluminates. The useful sources of YO₂, e.g. silicon oxide,include, as non-limiting examples, known forms of such oxide, e.g.silicic acid or silicon dioxide, alkoxy- or other compounds of silicon,including silica gel and silica hydrosol.

It will be understood that each oxide component utilized in the reactionmixture for this synthesis can be supplied by one or more essentialreactants and they can be mixed together in any order. For example, anyoxide can be supplied by an aqueous solution. The reaction mixture canbe prepared either batchwise or continuously. Crystal size andcrystallization time for the product composition comprising the MCM-47crystals will vary with the exact nature of the reaction mixtureemployed within the above limitations.

The bis(methylpyrrolidinium)-DIQUAT-4 directing agent has been found toeffectively stabilize the developing crystal framework of MCM-47 duringhydrothermal synthesis using the above high YO₂, high alkalinityreaction mixture. It also leads to a MCM-47 crystal framework capable ofan extremely wide range of YO₂ /X₂ O₃ mole ratios as shown herein.

The MCM-47 crystal composition prepared hereby has a characteristicX-ray diffraction pattern, including values substantially as set forthin Table 1, hereinafter.

                  TABLE 1                                                         ______________________________________                                        Interplanar d-Spacing, (A)                                                                     Relative Intensity (I/I.sub.o)                               ______________________________________                                        10.9 ± 0.15   vs                                                           6.91 ± 0.08   w                                                            6.23 ± 0.08   w                                                            5.18 ± 0.05   w-m                                                          4.90 ± 0.05   w                                                            4.35 ± 0.05   m                                                            4.17 ± 0.03   m                                                            3.86 ± 0.03   w                                                            3.81 ± 0.03   w                                                            3.78 ± 0.03   w                                                            3.67 ± 0.03   w                                                            3.57 ± 0.03   m                                                            3.48 ± 0.03   vs                                                           ______________________________________                                    

These X-ray diffraction data were collected with a Rigaku diffractionsystem, equipped with a graphite diffracted beam monochromator andscintillation counter, using copper K-alpha radiation. The diffractiondata were recorded by step-scanning at 0.02 degrees of two-theta, wheretheta is the Bragg angle, and a counting time of 1 second for each step.The interplanar spacings, d's, were calculated in Angstrom units (A),and the relative intensities of the lines, I/I_(o), where I_(o) isone-hundredth of the intensity of the strongest line, above background,were delivered with the use of a profile fitting routine (or secondderivative algorithm). The intensities are uncorrected for Lorentz andpolarization effects. The relative intensities are given in terms of thesymbols vs=very strong (75-100), s=strong (50-74), m=medium (25-49) andw=weak (0-24). It should be understood that diffraction data listed forthis sample as single lines may consist of multiple overlapping lineswhich under certain conditions, such as differences in crystallite sizesor very high experimental resolution or crystallographic change, mayappear as resolved or partially resolved lines. Typically,crystallographic changes can include minor changes in unit cellparameters and/or a change in crystal symmetry, without a change intopology of the structure. These minor effects, including changes inrelative intensities, can also occur as a result of differences incation content, framework composition nature and degree of pore filling,and thermal and/or hydrothermal history. It is noticed that the MCM-47crystals of this invention exhibit an X-ray diffraction pattern with thed-spacing maxima of MCM-47, but with slightly different relativeintensities.

The crystalline silicate MCM-47 prepared hereby has a compositioninvolving the molar relationship:

    X.sub.2 O.sub.3 :(y)YO.sub.2

wherein X is a trivalent element, such as aluminum, boron, iron, indiumand/or gallium, preferably aluminum; Y is a tetravalent element, such assilicon, tin and/or germanium, preferably silicon; and y is at leastabout 200, usually from about 400 to greater than about 3000, moreusually from about 500 to about 3000. In the as-synthesized form, thecrystalline silicate has a formula, on an anhydrous basis and in termsof moles of oxides per y moles of YO₂, as follows:

    (5-60)R.sub.2 O:(0-40)M.sub.2 O:X.sub.2 O.sub.3 :yYO.sub.2

wherein M and R are as defined above. The M and R components areassociated with the material as a result of their presence duringcrystallization, and are easily removed by post-crystallization methodshereinafter more particularly described.

Synthetic MCM-47 crystals prepared in accordance herewith can be usedeither in the as-synthesized form, the hydrogen form or anotherunivalent or multivalent cationic form. It can also be used in intimatecombination with a hydrogenating component such as tungsten, vanadium,molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noblemetal such as platinum or palladium where ahydrogenation-dehydrogenation function is to be performed. Suchcomponents can be exchanged into the composition, impregnated therein orphysically intimately admixed therewith. Such components can beimpregnated in or on to the MCM-47 such as, for example, by, in the caseof platinum, treating the material with a platinum metal-containing ion.Suitable platinum compounds for this purpose include chloroplatinicacid, platinous chloride and various compounds containing the platinumamine complex. Combinations of metals and methods for their introductioncan also be used.

Synthetic MCM-47 crystals, when employed either as an adsorbent or as acatalyst in a hydrocarbon conversion process, should be dehydrated atleast partially. This can be done by heating to a temperature in therange of from about 65° C. to about 315° C. in an inert atmosphere, suchas air, nitrogen, etc. and at atmospheric or subatmospheric pressuresfor between 1 and 48 hours. Dehydration can be performed at lowertemperature merely by placing the zeolite in a vacuum, but a longer timeis required to obtain a particular degree of dehydration. The thermaldecomposition product of the newly synthesized MCM-47 can be prepared byheating same at a temperature of from about 200° C. to about 550° C. forfrom 1 hour to about 48 hours.

The original cations, e.g. alkali or alkaline earth metal, of theas-synthesized material can be replaced in accordance with techniqueswell known in the art, at least in part, by ion exchange with othercations. Preferred replacing cations include metal ions, hydrogen ions,hydrogen precursor, e.g. ammonium, ions and mixtures thereof.Particularly preferred cations are those which render the materialcatalytically active, especially for certain hydrocarbon conversionreactions. These include hydrogen, rare earth metals and metals ofGroups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Tableof the Elements, especially gallium, indium and tin.

Typical ion exchange technique would be to contact the synthetic MCM-47material with a salt of the desired replacing cation or cations.Examples of such salts include the halides, e.g. chlorides, nitrates andsulfates.

Representative ion exchange techniques are disclosed in a wide varietyof patents including U.S. Pat. Nos. 3,140,249; 3,140,251; and 3,140,253.

Following contact with the salt solution of the desired replacingcation, the MCM-47 is then preferably washed with water and dried at atemperature ranging from 65° C. to about 315° C. and thereafter may becalcined in air or other inert gas at temperatures ranging from about200° C. to about 55° C. for periods of time ranging from 1 to 48 hoursor more to produce a catalytically-active thermal decomposition productthereof.

The crystalline silicate MCM-47 prepared by the instant invention isformed in a wide variety of particle sizes. Generally speaking, theparticles can be in the form of a powder, a granule, or a moldedproduct, such as extrudate having particle size sufficient to passthrough a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler)screen. In cases where the catalyst is molded, such as by extrusion, thecrystalline silicate can be extruded before drying or dried or partiallydried and then extruded.

In the case of many catalysts, it is desired to incorporate the crystalshereby prepared with another material resistant to the temperatures andother conditions employed in certain organic conversion processes. Suchmatrix materials include active and inactive materials and synthetic ornaturally occurring zeolites as well as inorganic materials such asclays, silica and/or metal oxides, e.g. alumina, titania and/orzirconia. The latter may be either naturally occurring or in the form ofgelatinous precipitates, sols or gels including mixtures of silica andmetal oxides. Use of a material in conjunction with the MCM-47, i.e.combined therewith, which is active, may enhance the conversion and/orselectivity of the catalyst in certain organic conversion processes.Inactive materials suitably serve as diluents to control the amount ofconversion in a given process so that products can be obtainedeconomically and orderly without employing other means for controllingthe rate or reaction. Frequently, crystalline catalytic materials havebeen incorporated into naturally occurring clays, e.g. bentonite andkaolin. These materials, i.e. clays, oxides, etc., function, in part, asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in a petroleum refinery the catalyst isoften subjected to rough handling, which tends to break the catalystdown into powder-like materials which cause problems in processing.

Naturally occurring clays which can be composited with the herebysynthesized crystalline material include the montmorillonite and kaolinfamilies which include the subbentonites, and the kaolins commonly knownas Dixie, McNamee, Georgia and Florida clays, or others in which themain mineral constituent is halloysite, kaolinite, dickite, nacrite oranauxite. Such clays can be used in the raw state as originally mined orinitially subjected to calcination, acid treatment or chemicalmodification.

In addition to the foregoing materials, the present crystals can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania, as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia. The matrix can be in the form of a cogel.A mixture of these components could also be used.

The relative proportions of finely divided crystalline material andmatrix vary widely with the crystalline material content ranging fromabout 1 to about 90 percent by weight, and more usually in the range ofabout 2 to about 50 percent by weight of the composite.

Employing a catalytically active form of the catalyst of this inventionwhich may contain additional hydrogenation components, reforming stockscan be reformed employing a temperature between about 370° C. and about540° C. The pressure can be between about 100 psig and about 1000 psig,but it is preferably between about 200 psig and about 700 psig. Theliquid hourly space velocity is generally between about 0.1 and about10, preferably between about 0.5 and about 4, and the hydrogen tohydrocarbon mole ratio is generally between about 1 and about 20,preferably between about 4 and about 12.

The catalyst can also be used for hydroisomerization of normalparaffins, when provided with a hydrogenation component, e.g. platinum.Hydroisomerization is carried out at a temperature between about 90° C.and 375° C., preferably about 145° C. to about 290° C., with a liquidhourly space velocity between about 0.01 and about 2, preferably betweenabout 0.25 and about 0.50, employing hydrogen such that the hydrogen tohydrocarbon mole ratio is between about 1:1 and about 5:1. Additionally,the catalyst can be used for olefin or aromatic isomerization, employinga temperature between about 200° C. and about 480° C.

The catalyst can also be used for reducing the pour point of gas oils.This reaction may be conducted at a liquid hourly space velocity betweenabout 10 and about 30 and at a temperature between about 425° C. andabout 595° C.

Other reactions which can be accomplished employing the catalyst of thisinvention containing a metal, e.g. platinum, includehydrogenation-dehydrogenation reactions and desulfurization reactions,olefin polymerization (oligomerization) and other organic compoundconversions such as the conversion of alcohols (e.g. methanol) tohydrocarbons, and the alkylation of aromatics (e.g. benzene).

In order to more fully illustrate the nature of the invention and themanner of practicing same, the following examples are presented. In theexamples, whenever absorption data are set forth for comparison ofsorptive capacities for water, cyclohexane and n-hexane, they weredetermined as follows:

A weighed sample of the calcined adsorbant was contacted with thedesired pure adsorbate vapor in an adsorption chamber, evacuated to 1 mmand contacted with 12 mm Hg of water vapor or 20 mm Hg of n-hexane, orcyclohexane vapor, pressures less than the vapor-liquid equilibriumpressure of the respective adsorbate at room temperature. The pressurewas kept constant (within about ±0.5 mm) by addition of absorbate vaporcontrolled by a manostat during the adsorption period, which did notexceed about 8 hours. As adsorbate was adsorbed by the sorbant material,the decrease in pressure caused the manostat to open a valve whichadmitted more adsorbate vapor to the chamber to restore the abovecontrol pressures. Sorption was complete when the pressure change wasnot sufficient to activate the manostat. The increase in weight wascalculated as the adsorption capacity of the sample in g/100 g ofcalcined adsorbant.

When Alpha Value is examined, it is noted that the Alpha Value is anapproximate indication of the catalytic cracking activity of thecatalyst compared to a standard catalyst and it gives the relative rateconstant (rate of normal hexane conversion per volume of catalyst perunit time). It is based on the activity of silica-alumina crackingcatalyst taken as an Alpha of 1 (Rate Constant=0.016 sec⁻¹). The AlphaTest is described in U.S. Pat. No. 3,354,078; in the Journal ofCatalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p.395 (1980), each incorporated herein by reference as to thatdescription. The experimental conditions of the test used herein includea constant temperature of 538° C. and a variable flow rate as describedin detail in the Journal of Catalysis, Vol. 61, p. 395.

EXAMPLE 1

A 2.88 gram quantity of NaOH pellets was dissolved in 138.4 gramsdeionized water. After all the NaOH had dissolved, 11.5 grams of theorganic template bis(methylpyrrolidinium)-DIQUAT-4 was dissolved in thebasic solution. This solution was then transferred to a 300 ml stainlesssteel autoclave. 48.0 grams of colloidal silica sol (30% SiO₂) weremixed into the solution in the autoclave and the resulting hydrogel wasstirred vigorously at room temperature for two minutes. The finalhydrogel is described by the mole ratios as follows:

    ______________________________________                                        SiO.sub.2 /Al.sub.2 O.sub.3 =                                                                 ∞                                                       OH.sup.-- /SiO.sub.2 =                                                                        0.30                                                          R/SiO.sub.2 =   0.10                                                          H.sub.2 O/SiO.sub.2 =                                                                         40                                                            Na.sup.+ /SiO.sub.2 =                                                                         0.30                                                          ______________________________________                                    

The autoclave was then sealed and heating and stirring were begunimmediately. The zeolite crystallization was carried out at 160° C. withstirring (400 rpm) for 4 days.

At the end of 4 days, the crystallization was terminated by quenchingthe autoclave to room temperature in a water-ice bath. The resultantzeolite product was filtered, washed in boiling deionized water andfinally filtered.

The crystalline product was dried under an infrared heat lamp in anairstream.

The product of this Example had the X-ray spectra shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Degrees       Interplanar                                                                              Relative                                             2-Theta       d-Spacing (A)                                                                            Intensity                                            ______________________________________                                         7.787        11.194     100.0                                                12.473        6.997      10.1                                                 13.937        6.264      5.7                                                  15.021        5.815      >1.0                                                 15.281        5.717      >1.0                                                 15.596        5.602      1.9                                                  16.513        5.293      >1.0                                                 16.655        5.248      8.2                                                  16.769        5.212      1.3                                                  16.830        5.194      1.9                                                  16.951        5.157      1.9                                                  17.664        4.950      4.4                                                  17.805        4.911      >1.0                                                 17.957        4.870      1.9                                                  20.015        4.374      11.4                                                 20.273        4.319      >1.0                                                 20.343        4.304      1.3                                                  20.497        4.272      1.9                                                  20.855        4.199      7.6                                                  21.804        4.019      1.9                                                  22.565        3.885      4.4                                                  22.824        3.841      >1.0                                                 22.891        3.830      3.8                                                  23.479        3.736      4.4                                                  23.667        3.706      >1.0                                                 23.778        3.689      3.2                                                  24.268        3.616      1.9                                                  24.348        3.604      1.9                                                  24.477        3.586      7.6                                                  24.963        3.517      2.3                                                  25.069        3.502      43.3                                                 25.831        3.400      7.0                                                  25.936        3.387      1.3                                                  26.136        3.362      5.7                                                  26.198        3.354      2.5                                                  26.295        3.342      5.1                                                  26.479        3.319      >1.0                                                 26.689        3.293      1.3                                                  26.824        3.277      >1.0                                                 26.938        3.263      >1.0                                                 27.021        3.253      >1.0                                                 27.168        3.236      1.3                                                  27.607        3.186      1.9                                                  27.894        3.153      1.3                                                  28.001        3.142      >1.0                                                 28.080        3.133      1.3                                                  28.554        3.082      1.9                                                  29.075        3.028      >1.0                                                 29.259        3.009      1.3                                                  29.420        2.993      1.9                                                  ______________________________________                                    

Table 3 presents details of Example 1 and additional examples of zeolitesyntheses over a very broad mixture SiO₂ /Al₂ O₃ range from about 90 tosilica-only (∞) with the organic directing agentsbis(methylpyrrolidinium)-DIQUAT-4 and bis(methylpyrrolidinium)-DIQUAT-3.The preparation of Example 1 was repeated for additional Examples 2through 9.

From the examples in Table 3 it was found that the novel zeolite MCM-47was synthesized when the mixture SiO₂ /Al₂ O₃ ratio of the hydrogel wasgreater than about 200/l with the organic template cationbis(methylpyrrolidinium)-DIQUAT-4. In Examples 8 and 9 when the mixtureSiO₂ /Al₂ O₃ ratio of the hydrogel was less than about 200/l, a zeoliteother than MCM-47 was crystallized with this same organic template.

The synthesis of zeolite MCM-47 is very specific with organic templatecations of the size of bis(methylpyrrolidinium)-DIQUAT-4. In Example 5when the organic template cation was bis(methylpyrrolidinium)-DIQUAT-3,only α-quartz was produced from the silica-only hydrogel.

                  TABLE 3                                                         ______________________________________                                        Crystallization of MCM-47                                                     160° C.; stirred                                                       Ex-  Mixture Composition                                                      am-  (Mole Ratios)                                                            ple  SiO.sub.2.sup.a                                                                       H.sub.2 O                                                                            OH   Na.sup.+                                                                           R.sup.b                                                                            Time,                                      No.  Al.sub.2 O.sub.3                                                                      SiO.sub.2                                                                            SiO.sub.2                                                                          SiO.sub.2                                                                          SiO.sub.2                                                                          Days  Product                              ______________________________________                                        1    ∞ 40     0.30 0.30 0.10 6     MCM-47                               2    ∞ 40     0.30 0.30 0.10 3     MCM-47                               3    ∞ 40     0.30 0.30 0.10 4     MCM-47                               4    ∞ 40     0.30 0.30 0.10 7     MCM-47                               5    300     40     0.30 0.31 0.10 4     MCM-47 +                                                                      zeolite other                                                                 than MCM-47                          6    500     40     0.30 0.31 0.10 4     MCM-47 +                                                                      zeolite other                                                                 than MCM-47                          7    ∞ 40     0.30 0.30 0.10 .sup. 7.sup.c                                                                       α-Quartz only                  8    180     40     0.30 0.31 0.10 6     Zeolite other                                                                 than MCM-47                          9     90     40     0.30 0.32 0.10 6     Zeolite other                                                                 than MCM-47                          ______________________________________                                         .sup.a Silica sol (30% SiO.sub.2)                                             ##STR1##                                                                      ##STR2##                                                                 

Table 4 lists the analytical results for the MCM-47 products produced inExamples 1-4 of Table 3. The data show that the organic templateremained intact within the product MCM-47 zeolite framework.

The MCM-47 compositions were calculated on the basis of 100 (SiO₂ +AlO₂⁻⁻) tetrahedra since the structure of new zeolite MCM-47 is unknown.There was a constant composition of nearly 5bis(methylpyrrolidinium)-DIQUAT-4 cations (R) per 100 tetrahedra in theMCM-47 products, indicating templating activity for the organic cation.

                                      TABLE 4                                     __________________________________________________________________________    Analyses of MCM-47 Samples                                                           C moles.sup.a                                                                      Moles per mole Al.sub.2 O.sub.3                                                          Composition.sup.b                                      Example No.                                                                          N Moles                                                                            N.sub.2 O:                                                                        Na.sub.2 O:                                                                       SiO.sub.2                                                                        Al/100 Td                                                                           Na.sup.+ /100 Td                                                                     N/100 Td                                                                            R.sup.c /100 Td                     __________________________________________________________________________    1      6.67 50.7                                                                              6.29                                                                               918                                                                             0.22  1.37   11.0  5.5                                 2      7.71 98.0                                                                              35.2                                                                              1840                                                                             0.11  3.82   10.6  5.3                                 3      7.12 73.9                                                                              16.4                                                                              1365                                                                             0.15  2.40   10.8  5.4                                 4      7.47 104 13.1                                                                              2089                                                                             0.09  1.25    9.9  4.9                                 __________________________________________________________________________     .sup.a Theor. C/N = 7/1                                                       .sup.b Based on 100 (SiO.sub.2 + AlO.sub.2.sup.-) tetrahedra (Td)             ##STR3##                                                                 

Changes and modifications in the specifically described embodiments canbe carried out without departing from the scope of the invention whichis intended to be limited only by the scope of the appended claims.

What is claimed is:
 1. A method for synthesizing crystalline materialexhibiting a characteristic X-ray diffraction pattern includingd-spacing maxima values, in Angstroms, as follows:10.9±0.15 6.91±0.086.23±0.08 5.18±0.05 4.90±0.05 4.35±0.05 4.17±0.03 3.86±0.03 3.81±0.033.78±0.03 3.67±0.03 3.57±0.03 3.48±0.03which comprises (i) preparing amixture capable of forming said material, said mixture comprisingsources of alkali or alkaline earth metal (M), an oxide of trivalentelement (X), an oxide of tetravalent element (Y), water andbis(methylpyrrolidinium)-DIQUAT-4 directing agent (R), and having acomposition, in terms of mole ratios, within the following ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                   200 to ∞                                                  H.sub.2 O/YO.sub.2                                                                            5 to 400                                                      OH.sup.- /YO.sub.2                                                                          0 to 1.0                                                        M/YO.sub.2    0 to 2.0                                                        R/YO.sub.2    0.005 to 2.0                                                    ______________________________________                                    

(ii) maintaining said mixture under sufficient conditions until crystalsof said material are formed; and (iii) recovering said crystallinematerial from step (ii), said recovered crystalline material containingsaid R.
 2. The method of claim 1 wherein said mixture has the followingcomposition ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                         300 to 10,000                                             H.sub.2 O/YO.sub.2  20 to 100                                                 OH.sup.-- /YO.sub.2 0.05 to 0.4                                               M/YO.sub.2          0.10 to 1.0                                               R/YO.sub.2          0.05 to 1.0.                                              ______________________________________                                    


3. The method of claim 1 wherein said mixture further comprises seedcrystals in sufficient amount to enhance synthesis of said crystallinematerial.
 4. The method of claim 3 wherein said seed crystals have thestructure of MCM-
 47. 5. The method of claim 1 wherein X is selectedfrom the group consisting of aluminum, boron, iron, gallium, indium andmixtures thereof, and said Y is selected from the group consisting ofsilicon, germanium, tin and mixtures thereof.
 6. The method of claim 1wherein X comprises aluminum and Y comprises silicon.
 7. A mixturecapable of forming crystals of MCM-47 structure upon crystallization,said mixture comprising sources of alkali or alkaline earth metal (M),trivalent element (X) oxide selected from the group consisting of oxideof aluminum, boron, iron, gallium, indium and mixtures thereof;tetravalent element (Y) oxide selected from the group consisting ofoxide of silicon, germanium, tin and mixtures thereof; water andbis(methylpyrrolidinium)-DIQUAT-4 (R), and having a composition, interms of mole ratios, within the following ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                          200 to ∞                                           H.sub.2 O/YO.sub.2   20 to 100                                                OH.sup.-- /YO.sub.2  0.05 to 0.4                                              M/YO.sub.2           0.10 to 1.0                                              R/YO.sub.2           0.05 to 1.0.                                             ______________________________________                                    


8. The method of claim 1 comprising replacing ions of the crystallinematerial recovered in step (iii), at least in part, by ion exchange withan ion or a mixture of ions selected from the group consisting ofhydrogen and hydrogen precursors, rare earth metals and metals fromGroups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII of the PeriodicTable of Elements.
 9. The method of claim 2 comprising replacing ions ofthe crystalline material recovered in step (iii), at least in part, byion exchange with an ion or a mixture of ions selected from the groupconsisting of hydrogen and hydrogen precursors, rare earth metals andmetals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII ofthe Periodic Table of Elements.
 10. The method of claim 8 wherein saidreplacing ion is hydrogen or a hydrogen precursor.
 11. The method ofclaim 9 wherein said replacing ion is hydrogen or a hydrogen precursor.12. The recovered crystalline material of claim
 1. 13. The recoveredcrystalline material of claim
 2. 14. The R-containing productcrystalline material of claim
 8. 15. The R-containing productcrystalline material of claim
 9. 16. The R-containing productcrystalline material of claim
 10. 17. The R-containing productcrystalline material of claim 11.